Isothermal Calorimetry

of Cement
The hydration process of cement is highly exothermic and is
typically measured in the milliwatt (mW) range.
TAM Air was originally designed for use in cement
calorimetry research.
TAM Air combines eight channels with a sensitivity of about
4 W.
TAM Air
Calorimetric Unit
General Heat Balance Equation
After calibration the following holds:
Rate of Heat
Production
(dQ/dt)
=
Heat flow
Monitored
by TAM
|
.
|

\
|
dt
dT
C
+
u
=
dt
dQ
Rate of Heat
Accumulation
+
Rate of Heat
Exchange
Rate of Heat
Production
=
u
|
.
|

\
|
dt
dQ
To
TS
|
.
|

\
|
dt
dT
C
The measured property
TAM Air
Fan
Heat detector
Fan
Heat detector
8 Channel calorimeter block
Thermostat
Air in
TAM Air Heat Detectors
Consist of small plates with
thermopiles (Seebeck Modules)
When the two sides of the plate are
exposed to different temperatures,
heat will flow from the warm to the
cold side
Same principle as TAM III
Sensitivity in W-mW range
Heat sink in contact with the air thermostat
Static Calibration
P (W)
Time
Calibration
Power OFF
Calibration Power ON
= set W pulse
Empty calorimeter or Accessory and Reference in position.
How to obtain t
The time until P/Po = 1/e = 0.37
) exp(
t
t
P P
o
=
P/Po = 1/e
Exponential heat exchange
Heatflow and Dynamically Corrected Data
For reactions where the slope of the heat flow time curve (dP
Raw
/dt) is
changing slowly the first part of the following formula can be used to
calculate the true response in heat flow (P
HF
) from the heat flow monitored
by the heat detector (P
Raw
) using the following formula. For fast reactions
an additional term is used to calculate P
Dyn
.
( )
2
2
2 1 2 1
dt
dP
dt
dP
P P
Raw Raw
Raw Dyn
t t t t + + + =
dt
dP
P P
Raw
Raw HF
t + =
The hydration process undergoes a
number of phases (Young, 1985)
(I) Rapid initial processes
(II) Dormant period
(III) Acceleration period
(IV) Retardation period
(V) Long term reactions
The phases have been described in more detail (Sandberg, 2002)
(I) Dissolution of ions and initial hydration
(II) Formation of ettringite
(III) Initiation of silicate hydration
(IV) Depletion of sulphate
Dr. P. Sandberg, Grace Construction Products, US (2002)
Basics of Cement Calorimetry
Portland Cement Basics
Silicates hydrate to give strength giving gel, glue
Aluminate and ferrite phases necessary to get a molten phase during production of
cement
Aluminates react rapidly, interact with admixtures, workability, set, early strength
development
Gypsum added during grinding to slow down aluminate hydration rate
Higher C
3
A , lower C
4
AF generally more reactive
Different sulfate forms have different solubility
ASTM Standard Method drafts available in 2008
C1679 (kinetics) C1679 (kinetics)
WK 4922 (heat of hydration) WK 4922 (heat of hydration)
Dr. P. Sandberg, Grace Construction Products, US (2002)
Isothermal calorimetry is sensitive and versatile tool for studying the
hydration process of cement.
The shape of the heat flow versus time curve reflects the hydration
process(es) of cement
The effect of an admixture is reflected in a change of the hydration
curve
The integrated heat flow time curve, i.e. the energy evolved is related
to the extent of hydration
Excellent experimental reproducibility.
Isothermal Calorimetry for Cements
Typical Cement Applications for Isothermal Calorimetry
Setting time and premature stiffening
Effect of contaminations
Effect of admixtures
Temperature dependency of cement hydration
Quality control
R&D
Dr. P. Sandberg, Grace Construction Products, US (2002)
Closed ampoules for long term
reactions.
Admix ampoule for early reactions
i.e. first 30-45 minutes.
Refer to EN 302 (Lars Wads)
Sample Handling
How to Perform Cement Hydration Measurements
Weigh ampoule and/or lid
Weigh cement powder (1-10g) and water (1-10g)
Mix well and mix for a consistent time (~1-3min)
Stirring rate can be important
Time zero important
Load and weigh cement paste into the ampoule
Load into TAM Air and come back in a few days
Most common test is 72 hour (or 3 day) hydration
Cement hydration completion after 28 days
ASTM Methods in 2008 - WK4922 or C1679 (kinetics)
Dr. Moro , Holcim Group Support, Switzerland (2002)
Isothermal Calorimetry Reproducibility
Only small differences between
cement lots when tested
without admixture
Very large differences between
cement lots when tested with
same admixture!!!

Water/cement ratio 0.5, 23 C,
water only

Water/cement ratio 0.5,
23 C, 1.0% water
reducing admixture by
weight of cement in all
samples
Dr. P. Sandberg, Grace Construction Products, US (2002)
Effect of Admixtures
Kinetics of Cement Hydration
Measurements at 20, 25 and 30 C
P reflects the rate of the process
Q reflects the extent of the process
P

(
m
W
)
Q

(
W
)
Time (h)
Dr. P. Vikegard, Thermometric AB, Sweden (2002)
Admix Ampoule Experiment Reproducibility
0.46hr
0.04hr
0.39hr
0.14hr
0.04hr
0.00
0.05
0.10
0.15
0.20
0.25
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w

(
W
/
g
)
0.0 0.2 0.4 0.6 0.8 1.0
Time (hr)
Stucco_w/c 0.50_1
Stucco_w/c 0.50_2
Stucco_w/c 0.50_5% Salt
Universal V4.4A TA Instruments
Calcium Sulfate Hemihydrate 1-2 g
powder mixed at w/c 0.50
5% NaCl solution
DI water
Admix Ampoule Experiment
0.00
0.02
0.04
0.06
0.08
0.10
0.12
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w

(
W
/
g
)
0.0 0.5 1.0 1.5 2.0
Time (hr)
Stucco w/c 0.35
Stucco w/c 0.50
Universal V4.4A TA Instruments
w/c =0.50
Calcium Sulfate Hemihydrate 1-2 g
mixed with DI water at w/c 0.50 and 0.35
w/c =0.35
Normalized Heat of Wetting/Mixing
(
m
W
/
g
)
Time (min)
100 120 140 160 180
0
10
20
30
FPC 9 FPC 9 FPC 3 FPC 3
Heat of wetting and stirring
Mix ~2.85 g cement solid with 1.38mL water
Differences in the heat of wetting/mixing observed for two different cement
powders. Mixed with DI water at w/c 0.48. Hydration plot shownon next slide.
Normalized Heat of Hydration
(
m
W
/
g
)
Time (hour)
12 24 36 48 60 72
0
1
2
3
4
5
FPC 9 FPC 9 FPC 3 FPC 3
Heat of hydration
Differences in the cement hydration profile observed. Mixed with DI water at w/c 0.48.
Mix ~2.85 g cement solid with 1.38mL water
Normalized Heat
(
J
/
g
)
Time (hour)
12 24 36 48 60 72
0
50
100
150
200
250
300
FPC 9 FPC 9 FPC 3 FPC 3
Mix ~2.85 g cement solid with 1.38mL water
Differences in the cement hydration profile observed. Mixed with DI water at w/c 0.48.
Mortar Normalized Heat of Wetting
0.00
0.01
0.02
0.03
0.04
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w
_
2

(
m
W
/
g
)
0.00
0.01
0.02
0.03
0.04
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w

(
W
/
g
)
1.00 1.25 1.50 1.75 2.00
Time (hr)
FPC 9_RMS 4 mortar
FPC 9_RMS 5 mortar
Universal V4.5A TA Instruments
Cement 1 w/ Sand B
Cement 1 w/ Sand A
1 g cement: 2.75 g sand: 0.475mL water
Injected DI water
Mortar Normalized Heat of Hydration
0.000
0.001
0.002
0.003
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w
_
2

(
m
W
/
g
)
0.000
0.001
0.002
0.003
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w

(
W
/
g
)
0 10 20 30 40 50 60 70
Time (hr)
FPC 9_RMS 4 mortar
FPC 9_RMS 5 mortar
Universal V4.5A TA Instruments
Cement 1 w/ Sand B
Cement 1 w/ Sand A
1 g cement: 2.75 g sand: 0.475mL water
Repeatability
Three different samples
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0 0.5 1 1.5 2 2.5 3 3.5 4
Time (weks)
R
e
l
a
t
i
v
e

s
p
e
c
i
f
i
c

h
e
a
t

f
l
o
w
Solid sample
Microhygrostat
Glass tube with
pure solvent or a
solvent saturated
by a salt (e.g. sat.
NaCl (aq))
Developed independently by: Angberg, Uppsala University and Bystrm, Astra Zeneca (1992)
Other Calorimetric Methods for the Study of Cement
Adiabatic calorimetry or semi-adiabatic calorimetry
Sample is placed in insulation made of polystyrene. One example of a
semi-adiabatic calorimeter is the Nordic hkassen that was
investigated in NORDTEST-studies: NT 821 and NT Build 388.
Solution calorimetry
ASTM C186
Total heat of hydration at a certain time is determined as the
difference between the liberated heat when an un-hydrated sample
and the sample under investigation is dissolved in a mixture of
hydrofluoric acid and nitric acid.
This old measurement technique is described in ASTM C186, prEN
196-8, and SS B1 1960.
This method is time-consuming, costly and dangerous, but still in use.
Isothermal Calorimetry (heat flow) versus Semi-Adiabatic
Isothermal calorimeters directly measure the heat production
rate that is proportional to the rate of the reaction
adiabatic calorimeters measure temperature change and
that is recalculated to give heat produced
Heat capacity of the sample is required for adiabatic
calorimetry and not for isothermal
Isothermal calorimeters are very stable and need not be
calibrated more than a few times a year
adiabatic calorimeters are often calibrated before each run.
The temperature never increases to unrealistic temperatures
in an isothermal calorimeter. The structure and thus the
properties of the hardened cement paste depend on the
temperature of hydration.
A main benefit of isothermal calorimetry is that the hydration
process of the cement is monitored continuously with
multiple samples from the start of the measurements.
Analysis in laboratory environment
Multiple channels (sample and reference) for parallel
analysis
Built in calibration heaters for automated calibrations
Sample temperature can be assumedisothermal
Very sensitive calorimeter(s) with the ability to load up to
20 mL volume samples
Compare heat flow stability/sensitivity.
Admix accessory to study initial hydration.
Software includes data analysis
Isothermal Calorimetry
AN 22014 Hydroscopic powders a microcalorimetricassessment of
cement
AN 314-01 The Study of Cement Hydration by Isothermal Calorimetry
AN 314-05 Optimization of sulfate- Part I without admixture
AN 314-06 Optimization of cement sulfatePart II with admixture
AN 314-07 Effect of carboxylic acids on the hydration of calcium sulfate
hemihydratepastes
EN 302 Using the Admix ampoule for cement hydration measurements
ASTM Methods in 2008 - WK4922 or C1679 (kinetics)
Applications of an eight-channel isothermal conduction calorimeter for
cement hydration studies. By Lars Wads, Cement International 2005
Suggested Readings